CN103894047A - Flue gas pollutant control integrated purifying and recycling process - Google Patents
Flue gas pollutant control integrated purifying and recycling process Download PDFInfo
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- CN103894047A CN103894047A CN201410094498.2A CN201410094498A CN103894047A CN 103894047 A CN103894047 A CN 103894047A CN 201410094498 A CN201410094498 A CN 201410094498A CN 103894047 A CN103894047 A CN 103894047A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a flue gas pollutant control integrated purifying and recycling process, aiming to remove SOx, NOx and mercury in flue gas at the same time. According to the process, three kinds of emission control systems, namely a dry method sodium bicarbonate system, a wet method sodium bicarbonate system and an oxidizing agent system are combined together organically so as to achieve performance complementation, and very high removing rate can be achieved on various pollutants in flue gas. Meanwhile, the pollutants are converted into a useful chemical engineering product, namely sulphur, and no waste water, waste residue or other waste is emitted.
Description
Technical field
The present invention relates to flue gas desulfurization and denitrification technical field, be specifically related to a kind of flue gas pollutant control integrated purifying recovery process.
Background technology
In view of the long-term existence of China taking coal as main energy resource structure, and process of industrialization high speed development in recent years, oxysulfide (SOx) and nitrogen oxide (NOx) have become China's Air Pollutants, and with the various ways such as acid rain, haze, ecological environment has been caused to heavy damage, whole national economy life has been caused to great negative effect.
Flue gas desulfurization and denitrification is the main measure of air contaminant treatment.Flue gas desulfurization technique is a lot of both at home and abroad at present, as limestone-gypsum method, ammonia process, two alkaline process, rotary spraying technique etc., wherein from the desulfur technology of industrialization, though have that floor space is large, operating cost is high, easy obstruction, desulfurizing byproduct difficulty are put, secondary pollution problems, and and be unwell to China's national situation, but due to history, account for the limestone-gypsum method that is still of absolute leading position.And aspect gas denitrifying technology, selective catalytic reduction method (SCR), SNCR method (SNCR), electron beam irradiation method, impulse electric corona plasma method, red-hot carbon reduction method, low temperature normal atmosphere plasma decomposition methods etc. are wherein general with SCR method denitration application again.
And at present, in the world application more widely flue gas desulfurization and denitrification technology be utilize above-mentioned traditional flue gas desulfurization technique and SCR denitration technology combined, with reach can desulphurization denitration object.This technology can remove NOx more than more than 90% SOx and 80%, but this method in fact remains being used in combination of independent desulphurization and denitration technology, more have the disadvantage that above-mentioned desulphurization and denitration technology exists concurrently, failed to break away from that technological process is long, investment is large, operating cost is high, Technical Economy is poor, easily cause secondary pollution problems.
And for normal another important pollution mercury existing in flue gas, though the wet desulphurization devices such as limestone-gypsum method can be removed part Hg in flue gas
2+, but for water-fast Hg
0catch effect not remarkable.Also there is no at present the maturation process of demercuration.
Therefore, develop, apply a kind of technology to realize the synchronous purification techniques up to standard of Novel flue gas that removes SOx, NOx and mercury in whole system simultaneously, and make it have technological process shorter, invest low, purification efficiency is high, operating cost is low, can evade the advantages such as secondary pollution, just becomes the inevitable development trend of smoke gas treatment technology.
Application number is 201310277794.1, and name is called the application for a patent for invention of system and device and the method for sulphur " reclaim sulfur dioxide from flue gas produce ", discloses from the apparatus and method of off-gas recovery sulfur dioxide sulphur processed.This device forms by absorbing pyrolysis, reduction, three unit of Crouse.Absorbing pyrolysis unit is mainly made up of cooling tower, absorption tower, clarifier, circulating pump, regeneration pyrolysis groove, poor rich liquid heat exchanger; Reduction unit is made up of mixed gas generation systems, reduction reactor, sulfur condenser; Crouse unit is made up of claus reaction device, sulfur condenser; Method for absorb pyrolysis unit to flue gas absorb, pyrolysis obtains pure sulfur dioxide gas, reduction unit taking catalytic reaction by Sulphur Dioxide as simple substance sulphur.This patent is out sulfur dioxide by the sulfur dioxide desorption in solution, and is sulphur by sulphur dioxide reduction.The equipment great majority that use are special material, invest high; In the time that desorption effect is poor, desulfurized effect is poor; The steam that desorb consumes is high; Desorption process is intermittent-heating, need to use heat exchanger, and generally dust-laden all of flue gas easily stops up heat exchanger.
Summary of the invention
The present invention, in order to realize SOx, the NOx and the mercury that remove in flue gas simultaneously, provides a kind of flue gas pollutant control integrated purifying recovery process.Technique is organically combined dry method sodium acid carbonate, wet method sodium acid carbonate and three kinds of emission control systems of oxidant, realizes performance complement, and each pollutant in flue gas is had to very high removal efficiency.Meanwhile, pollutant is converted into useful chemical products---sulphur, without waste water, the discharge of waste residue the like waste.
For achieving the above object, the present invention adopts following technical scheme:
Flue gas pollutant control integrated purifying recovery process, is characterized in that: concrete steps are as follows:
A, flue gas and sodium bicarbonate powder are sent into circulating fluid bed reactor continuously, flue gas makes sodium bicarbonate powder be fluidisation state reaction with it, or sodium bicarbonate powder is directly sprayed into flue and smoke reaction, tentatively remove sulfureous in flue gas oxide and nitrogen oxide.
Sodium acid carbonate is decomposes in circulating fluid bed reactor, generates sodium carbonate, water and carbon dioxide, and the sulfur and nitrogen oxides in sodium carbonate absorption flue gas also reacts, thereby generates sodium sulphate and sodium nitrate, completes preliminary desulphurization denitration.
In the situation that flue gas flow is less (flue gas flow is less than 1,000,000 cubic meters/hour conventionally), A step can not used circulating fluid bed reactor, and adopt, sodium bicarbonate powder is directly sprayed into flue, with smoke reaction, realize and tentatively remove sulfur and nitrogen oxides.
B, the flue gas after the preliminary desulphurization denitration of A step is sent into the desulfurization section on absorption tower, utilized sodium bicarbonate aqueous solution to spray from top as absorption liquid, remove oxysulfide and other acidic components in flue gas; Flue gas after desulfurization enters the denitration section on absorption tower, utilizes containing the oxidizing agent solution of sodium acid carbonate and sprays from top as absorption liquid, further removes the nitrogen oxide in flue gas, and the flue gas after purification is discharged from the top on absorption tower; Merge the absorption liquid that discharge desulfurization section and denitration section bottom, and filter, obtain filtrate.
SO in flue gas
2content is reduced to 50 mg/m
3below, other sour gas in flue gas have been removed simultaneously.Nitrogen oxides in effluent is after oxidant oxidation, and NO becomes the NO that can absorb
2, then absorb NO with sodium acid carbonate
xcontent can be reduced to 100 mg/m
3below; Meanwhile, can also be by water-fast Hg in flue gas
0be oxidized to Hg through oxidant
2+, then wash seizure by sodium acid carbonate, and with the form filtering and removing of mercurous solid.
Oxidant of the present invention adopts in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide the aqueous solution of any one or several mixtures.
Preferably, the solid reaction product of discharging bottom circulating fluid bed reactor is dissolved, filtered, obtained filtrate, after merging with B step gained filtrate, delivered to again C step process.
C, the crystallization of B step gained concentrating filter liquor, obtain solid sodium salt, sends into reductor, under the effect of reducing agent, is reduced to vulcanized sodium; Reductor molten mixture out, through Quench, dissolving, filtration, washing, gained clear liquid is sodium sulfide solution; The rich CO that reductor is discharged
2gas, after waste heat boiler reclaims its heat generation steam, is delivered to next step processing.
Preferably, described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
D, in C step gained sodium sulfide solution, add sodium acid carbonate, will react gained H
2s gas is sent into claus oven, manufactures sulfur product; By reaction gained sodium carbonate liquor send to C step in rich CO
2gas reaction, obtains sodium acid carbonate and recycles.
In absorption tower of the present invention, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
Flue gas after purification of the present invention discharges after demister demist.
Choice for use sodium acid carbonate of the present invention, instead of directly use sodium carbonate.Utilizing sodium hydrogen carbonate powder decomposes in circulating fluid bed reactor or flue is sodium carbonate, for porous mass, absorption sulfureous in flue gas oxide and oxynitrides, particularly oxynitrides is had to strong suction-operated, after absorption, there is surface reaction, generate sodium sulphate and sodium nitrate, reach the object of desulphurization denitration.
The particle diameter of sodium bicarbonate powder of the present invention is 10 ~ 300 μ m, increases specific area, improves adsorption effect, has ensured that removal efficiency is high.
The straying quatity of described sodium bicarbonate powder sprays into according to stoichiometric 0.8 ~ 1.3 times, when ensureing high removal efficiency, can not cause the waste of sodium acid carbonate.
The fusion pool temperature of reductor of the present invention is 927～1038 DEG C, makes dry products fully melting and mixing in pond.
Reducing agent of the present invention is the one or more combination of carbon containing or hydrogeneous solid, gas, liquid fuel.Comprise natural gas, coke-stove gas, generation coal gas, CO, hydrogen, coal, coke, oil, tar, petroleum coke.
Preferably, described reducing agent is stoichiometric 1.1 ~ 1.5 times, can keep the percent reduction that contains sulfosalt more than 95%.
Preferably, described reducing agent is coal dust, and raw material is easy to get, and does not need to prepare separately the facilities such as coal storage, pulverizing, conveying, reduced investment.
Preferably, in the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 50 ~ 100g/l.The advantage of doing is like this: on the one hand, the flow of interpolation is less, has saved electric energy; On the other hand, because the flow adding is little, the raffinate flow of discharging after reaction is just little, the post processing expense of further having saved electric energy and raffinate.
Preferably, in the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 5 ~ 50g/l, the strict concentration of lye of controlling, be conducive to reduce the consumption of sodium acid carbonate, when further having saved cost, ensure nitrogen oxide and water-fast Hg in flue gas
0after oxidized, fully absorbed by sodium acid carbonate, effectively remove nitrogen oxide and mercury.
The tail gas of claus oven of the present invention returns to circulating fluid bed reactor or flue after burning and reclaiming heat with waste heat boiler, without independent exhaust gas processing device, and small investment, SR is low, does not need strictly to control parameter.
This technique and other technique are as the comparison of lime stone-gypsum method: discarded object is little; Product is valuable sulphur and steam, good in economic efficiency, there is no secondary pollution.
For burners such as coal-burning boiler, cement kiln, incinerators, before described A step, in the burner hearth of burner, temperature is, in the region of 850～1150 DEG C, to spray into ammoniacal liquor or urea liquid as reducing agent, be nitrogen by part reduction of nitrogen oxide in flue gas, realize preliminary denitration.
Beneficial effect of the present invention is:
1, flue gas pollutant control integrated purifying recovery process of the present invention is organically combined dry method sodium acid carbonate, wet method sodium acid carbonate and three kinds of emission control systems of oxidant, realize performance complement, each pollutant in flue gas is had to very high removal efficiency.Can be by the SO in flue gas
2be reduced to 50 mg/m
3below, remove other remaining sour gas in flue gas simultaneously; Can be by the NO in flue gas
xbe reduced to 100 mg/m
3below, effectively remove the Hg in flue gas simultaneously
2+and water-fast Hg
0.Realized the synchronous purification techniques up to standard of Novel flue gas that simultaneously removes SOx, NOx and mercury in whole system, and make it have technological process shorter, invest low, purification efficiency is high, operating cost is low, can evade the advantages such as secondary pollution.
2, choice for use sodium acid carbonate of the present invention is as absorbent, instead of directly uses sodium carbonate.After utilizing sodium bicarbonate powder to spray into circulating fluid bed reactor or flue, there is thermal decomposition for sodium carbonate, for porous mass, absorption sulfureous in flue gas oxide and oxynitrides, particularly oxynitrides is had to strong suction-operated, after absorption, there is surface reaction, generate sodium nitrate and sodium sulphate, reach the object of desulphurization denitration.Sodium acid carbonate is renewable to be recycled, and does not have secondary pollution.
3, strictly to control the particle diameter of sodium bicarbonate powder be 10 ~ 300 μ m in the present invention, there is high-specific surface area, the sodium carbonate forming after decomposes is cellular, thereby further increase specific area, improve and the contact area of flue gas, strengthened adsorption effect and high removal efficiency to oxysulfide and oxynitrides.
4, production technology of the present invention, in separate absorbent agent sodium acid carbonate, is produced high value-added product by chemical process---sulphur.After sodium acid carbonate sulfur dioxide absorption, form sodium sulfite/metabisulfite solution, finally from wherein isolating sodium sulfite and sodium sulphate, and adopt reducing agent to be reduced to vulcanized sodium, and vulcanized sodium and sodium acid carbonate react and generate hydrogen sulfide and sodium carbonate, and hydrogen sulfide is produced sulphur by claus reaction.This production technology is not used heat exchanger, can not stop up by generation equipment, and without waste water, the discharge of waste residue the like waste, product is valuable sulphur and steam, good in economic efficiency, there is no secondary pollution,
5, the present invention selects sodium acid carbonate as absorbent, and the rich CO that reductor is discharged
2gas reclaims its heat to produce after steam through waste heat boiler, then absorbs CO by sodium carbonate
2, separate and obtain sodium acid carbonate and recycle.This technique does not need to consume steam substantially, and energy consumption is low, good in economic efficiency.
6, the mass concentration of control sodium acid carbonate of the present invention in oxidizing agent solution is 5-50g/l, by strict control concentration of lye, reduces the consumption of sodium acid carbonate, in further having saved cost, ensures nitrogen oxide and water-fast Hg in flue gas
0oxidized fully absorbed by sodium acid carbonate afterwards, effectively removes nitrogen oxide and mercury.
7, the use amount of reducing agent of the present invention is stoichiometric 1.1 ~ 1.5 times, can keep the percent reduction that contains sulfosalt more than 95%, has ensured that the productive rate of sulphur reaches more than 98%.
8, the tail gas of claus oven of the present invention returns to circulating fluid bed reactor or flue after burning and reclaiming heat with waste heat boiler, without independent exhaust gas processing device, and small investment, SR is low, does not need strictly to control parameter, simple to operate.
9, the present invention is before A step, in the burner hearth of burner, temperature is in the region of 850～1150 DEG C, spray into ammoniacal liquor or urea liquid, for burners such as coal-burning boiler, incinerator, cement kilns, adding above-mentioned reducing agent is nitrogen by part reduction of nitrogen oxide in flue gas, realize preliminary denitration, further improve the removal of nitrogen oxide rate of technique.
Brief description of the drawings
Fig. 1 is the flow chart of flue gas pollutant control integrated purifying recovery process of the present invention.
Detailed description of the invention
Below in conjunction with detailed description of the invention, essentiality content of the present invention is described in further detail.
Embodiment 1
Flue gas pollutant control integrated purifying recovery process, concrete steps are as follows:
A, flue gas and sodium bicarbonate powder are sent into circulating fluid bed reactor continuously, flue gas makes sodium bicarbonate powder be fluidisation state reaction with it, tentatively removes sulfureous in flue gas oxide and nitrogen oxide;
B, the flue gas after the preliminary desulphurization denitration of A step is sent into the desulfurization section on absorption tower, utilized sodium bicarbonate aqueous solution to spray from top as absorption liquid, remove oxysulfide and other acidic components in flue gas; Flue gas after desulfurization enters the denitration section on absorption tower, utilizes containing the oxidizing agent solution of sodium acid carbonate and sprays from top as absorption liquid, further removes the nitrogen oxide in flue gas, and simultaneous oxidation removes Elemental Mercury; Flue gas after purification is discharged from the top on absorption tower; Merge the absorption liquid that discharge desulfurization section and denitration section bottom, and filter, obtain filtrate;
C, the crystallization of B step gained concentrating filter liquor, obtain solid sodium salt, sends into reductor, under the effect of reducing agent, is reduced to vulcanized sodium; Reductor molten mixture out, through Quench, dissolving, filtration, washing, gained clear liquid is sodium sulfide solution; The rich CO that reductor is discharged
2gas, after waste heat boiler reclaims its heat generation steam, is delivered to next step processing;
D, in C step gained sodium sulfide solution, add sodium acid carbonate, will react gained H
2s gas is sent into claus oven, manufactures sulfur product; By reaction gained sodium carbonate liquor send to C step in rich CO
2gas reaction, obtains sodium acid carbonate and recycles.
Embodiment 2
Flue gas pollutant control integrated purifying recovery process, concrete steps are as follows:
A, sodium bicarbonate powder is directly sprayed into flue and smoke reaction, tentatively remove sulfureous in flue gas oxide and nitrogen oxide;
B, the flue gas after the preliminary desulphurization denitration of A step is sent into the desulfurization section on absorption tower, utilized sodium bicarbonate aqueous solution to spray from top as absorption liquid, remove oxysulfide and other acidic components in flue gas; Flue gas after desulfurization enters the denitration section on absorption tower, utilizes containing the oxidizing agent solution of sodium acid carbonate and sprays from top as absorption liquid, further removes the nitrogen oxide in flue gas, and simultaneous oxidation removes Elemental Mercury; Flue gas after purification is discharged from the top on absorption tower; Merge the absorption liquid that discharge desulfurization section and denitration section bottom, and filter, obtain filtrate;
C, the crystallization of B step gained concentrating filter liquor, obtain solid sodium salt, sends into reductor, under the effect of reducing agent, is reduced to vulcanized sodium; Reductor molten mixture out, through Quench, dissolving, filtration, washing, gained clear liquid is sodium sulfide solution; The rich CO that reductor is discharged
2gas, after waste heat boiler reclaims its heat generation steam, is delivered to next step processing;
D, in C step gained sodium sulfide solution, add sodium acid carbonate, will react gained H
2s gas is sent into claus oven, manufactures sulfur product; By reaction gained sodium carbonate liquor send to C step in rich CO
2gas reaction, obtains sodium acid carbonate and recycles.
Embodiment 3
The embodiment of the present embodiment is substantially the same manner as Example 1, on this basis:
The solid reaction product that described circulating fluid bed reactor bottom is discharged is dissolved, is filtered, and obtains filtrate, after merging, delivers to C step process with B step gained filtrate again.
Embodiment 4
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
Embodiment 5
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 20 μ m.
Embodiment 6
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 10 μ m.
The fusion pool temperature of described reductor is 927 DEG C.
Embodiment 7
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 300 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 0.8 times.
The fusion pool temperature of described reductor is 1038 DEG C.
Embodiment 8
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
Embodiment 9
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 70 μ m.
Embodiment 10
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 80 μ m.
The fusion pool temperature of described reductor is 925 DEG C.
Embodiment 11
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 120 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 0.85 times.
The fusion pool temperature of described reductor is 1036 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 55g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 26g/l.
Embodiment 12
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 50 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.3 times.
The fusion pool temperature of described reductor is 1020 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 50g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 5g/l.
Embodiment 13
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 120 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.0 times.
The fusion pool temperature of described reductor is 956 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 80g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 50g/l.
Described reducing agent is coal dust.
Embodiment 14
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 120 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 0.9 times.
The fusion pool temperature of described reductor is 1020 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 72g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 10g/l.
Described reducing agent is coke.
Described reducing agent is stoichiometric 1.3 times.
Embodiment 15
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 200 μ m.
The fusion pool temperature of described reductor is 1012 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 90g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 40g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.1 times.
Embodiment 16
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 180 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 0.85 times.
The fusion pool temperature of described reductor is 986 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 65g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 30g/l.
Described reducing agent is natural gas.
Described reducing agent is stoichiometric 1.2 times.
The tail gas of described claus oven returns to circulating fluid bed reactor after burning and reclaiming heat with waste heat boiler.
Embodiment 17
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 250 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 0.9 times.
The fusion pool temperature of described reductor is 1022 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 75g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 25g/l.
Described reducing agent is coal dust and coke.
Described reducing agent is stoichiometric 1.5 times.
The tail gas of described claus oven returns to circulating fluid bed reactor after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
The flow that flue gas of the present invention enters absorption tower is millions of cubic meters/hour.
Before described A step, in the burner hearth region of 1100 DEG C of burner, spray into urea liquid.
Embodiment 18
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 250 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.0 times.
The fusion pool temperature of described reductor is 1022 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 75g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 25g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.5 times.
The tail gas of described claus oven returns to circulating fluid bed reactor after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
The flow that flue gas of the present invention enters absorption tower is millions of cubic meters/hour.
Before described A step, in the burner hearth region of 1000 DEG C of burner, spray into urea liquid.
Embodiment 19
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 150 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.1 times.
The fusion pool temperature of described reductor is 1010 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 65g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 35g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.5 times.
The tail gas of described claus oven returns to circulating fluid bed reactor after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
The flow that flue gas of the present invention enters absorption tower is millions of cubic meters/hour.
Before described A step, in the burner hearth region of 850 DEG C of burner, spray into ammoniacal liquor.
Embodiment 20
The embodiment of the present embodiment is substantially the same manner as Example 3, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 50 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.15 times.
The fusion pool temperature of described reductor is 1030 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 86g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 28g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.5 times.
The tail gas of described claus oven returns to circulating fluid bed reactor after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
The flow that flue gas of the present invention enters absorption tower is millions of cubic meters/hour.
Before described A step, in the burner hearth region of 1150 DEG C of burner, spray into ammoniacal liquor.
Embodiment 21
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 230 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.05 times.
The fusion pool temperature of described reductor is 1015 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 85g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 23g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.25 times.
The tail gas of described claus oven returns to flue and purifies recovery after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
Before described A step, in the burner hearth region of 1010 DEG C of burner, spray into urea liquid.
Embodiment 22
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 160 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.15 times.
The fusion pool temperature of described reductor is 1015 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 95g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 35g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.35 times.
The tail gas of described claus oven returns to purify and reclaims after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
Before described A step, in the burner hearth region of 875 DEG C of burner, spray into urea.
Embodiment 23
The embodiment of the present embodiment is substantially the same manner as Example 2, on this basis:
Described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
In described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
In described A step, the particle diameter of sodium bicarbonate powder is 135 μ m.
In described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 1.25 times.
The fusion pool temperature of described reductor is 1026 DEG C.
In the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 96g/l.
In the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 15g/l.
Described reducing agent is coal dust.
Described reducing agent is stoichiometric 1.35 times.
The tail gas of described claus oven returns to purify and reclaims after burning and reclaiming heat with waste heat boiler.
Oxidant of the present invention adopts the solution of one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
Before described A step, in the burner hearth region of 1050 DEG C of burner, spray into urea.
Flue gas pollutant control integrated purifying recovery process of the present invention, decontamination effect and cost compare with prior art, see the following form:
As can be seen here, flue gas pollutant integrated purifying recovery process of the present invention is organically combined dry method sodium acid carbonate, wet method sodium acid carbonate and three kinds of emission control systems of oxidant, to the removal efficiency of flue gas pollutant apparently higher than prior art.The present invention has not only realized the synchronous purification techniques up to standard of Novel flue gas that simultaneously removes SOx, NOx and mercury in whole system, pollutant is converted into useful chemical products---sulphur simultaneously, and productive rate, up to more than 98%, discharges without waste water, waste residue the like waste.Whole technique have flow process short, invest low, purification efficiency is high, operating cost is low, can evade the advantages such as secondary pollution.
Claims (15)
1. flue gas pollutant control integrated purifying recovery process, is characterized in that: concrete steps are as follows:
A, flue gas and sodium bicarbonate powder are sent into circulating fluid bed reactor continuously, flue gas makes sodium bicarbonate powder be fluidisation state reaction with it, or sodium bicarbonate powder is directly sprayed into flue and smoke reaction, tentatively remove sulfureous in flue gas oxide and nitrogen oxide;
B, the flue gas after the preliminary desulphurization denitration of A step is sent into the desulfurization section on absorption tower, utilized sodium bicarbonate aqueous solution to spray from top as absorption liquid, remove oxysulfide and other acidic components in flue gas; Flue gas after desulfurization enters the denitration section on absorption tower, utilizes containing the oxidizing agent solution of sodium acid carbonate and sprays from top as absorption liquid, further removes the nitrogen oxide in flue gas, and the flue gas after purification is discharged from the top on absorption tower; Merge the absorption liquid that discharge desulfurization section and denitration section bottom, and filter, obtain filtrate;
C, the crystallization of B step gained concentrating filter liquor, obtain solid sodium salt, sends into reductor, under the effect of reducing agent, is reduced to vulcanized sodium; Reductor molten mixture out, through Quench, dissolving, filtration, washing, gained clear liquid is sodium sulfide solution; The rich CO that reductor is discharged
2gas, after waste heat boiler reclaims its heat generation steam, is delivered to next step processing;
D, in C step gained sodium sulfide solution, add sodium acid carbonate, will react gained H
2s gas is sent into claus oven, manufactures sulfur product; By reaction gained sodium carbonate liquor send to C step in rich CO
2gas reaction, obtains sodium acid carbonate and recycles.
2. flue gas pollutant control integrated purifying recovery process according to claim 1, it is characterized in that: the solid reaction product that described circulating fluid bed reactor bottom is discharged is dissolved, filters, obtain filtrate, after merging with B step gained filtrate, deliver to again C step process.
3. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: described reductor molten mixture is out after Quench, dissolving, filtration, washing, and gained solid waste is sent to boiler and made fuel.
4. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: in described absorption tower, the absorption liquid of desulfurization section and denitration section reclaims respectively and recycles.
5. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: in described A step, the particle diameter of sodium bicarbonate powder is 10 ~ 300 μ m.
6. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: in described A step, the straying quatity of sodium bicarbonate powder sprays into according to stoichiometric 0.8 ~ 1.3 times.
7. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: the fusion pool temperature of described reductor is 927～1038 DEG C.
8. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: in the desulfurization section on described absorption tower, the mass concentration of sodium bicarbonate solution is 50 ~ 100g/l.
9. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: in the denitration section on described absorption tower, the mass concentration of sodium acid carbonate in oxidizing agent solution is 5 ~ 50g/l.
10. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: described reducing agent is any one or several combination of carbon containing or hydrogeneous solid, gas, liquid fuel.
11. flue gas pollutant control integrated purifying recovery process according to claim 10, is characterized in that: described reducing agent is stoichiometric 1.1 ~ 1.5 times.
12. flue gas pollutant control integrated purifying recovery process according to claim 11, is characterized in that: described reducing agent is coal dust.
13. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: the tail gas of described claus oven returns to circulating fluid bed reactor after burning and reclaiming heat with waste heat boiler or flue purifies recovery.
14. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: the oxidant in described B step is the aqueous solution of any one or several mixtures in potassium permanganate, sodium chlorite, clorox, calcium hypochlorite, hydrogen peroxide, chlorine dioxide.
15. according to the flue gas pollutant control integrated purifying recovery process described in claim 1 or 2, it is characterized in that: before described A step, in the burner hearth of burner, temperature is, in the region of 850～1150 DEG C, to spray into ammoniacal liquor or urea liquid.
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